CN112259446A - 高效制备氮化镓衬底的方法 - Google Patents
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
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Abstract
本发明公开了一种高效制备氮化镓衬底的方法，其特征在于：在硅衬底正反两面上用卤化物气相外延法生长氮化镓厚膜，控制生长条件，使双面氮化镓厚膜的厚度基本相同，酸或碱溶液腐蚀去除硅衬底，可以得到两片氮化镓厚膜衬底。本发明提出了利用硅衬底正反双面同时外延GaN厚膜，控制生长条件使得两面外延的氮化镓厚度相等或相近、分布均匀，这样两面外延的氮化镓对于硅衬底的应力减弱或相互抵消，从而得到高质量低应力GaN厚膜的方法。生长完成后的样品在碱溶液或酸溶液中进行腐蚀即可得到2片氮化镓衬底。
Description
技术领域
本发明涉及到一种高效制备氮化镓衬底的方法，属于半导体材料技术领域。
背景技术
以GaN及InGaN、AlGaN合金材料为主的III-V族氮化物材料(又称GaN基材料)是近几年来国际上倍受重视的新型半导体材料。GaN基材料是直接带隙宽禁带半导体材料，具有1.9—6.2eV之间连续可变的直接带隙，优异的物理、化学稳定性，高饱和电子漂移速度，高击穿场强和高热导率等优越性能，在短波长半导体光电子器件和高频、高压、高温微电子器件制备等方面具有重要的应用，用于制造比如蓝、紫、紫外波段发光器件、探测器件，高温、高频、高场大功率器件，场发射器件，抗辐射器件，压电器件等。
GaN单晶的熔点高达2300℃，分解点在900℃左右，生长需要极端的物理环境，而且大尺寸GaN单晶无法用传统晶体生长的方法得到。所以大多数的GaN薄膜都是在异质衬底上外延得到的。目前应用于半导体技术的GaN主要是采用异质外延方法在蓝宝石、SiC或Si等衬底上制备。在异质外延中，由于GaN材料和异质衬底之间存在较大的晶格失配和热膨胀系数失配，得到的GaN外延层中会有应力并产生处于108-109/cm2量级的位错密度，这些缺陷降低了外延层的质量，限制了GaN材料的热导率、电子饱和速度等参数，大大影响了器件的可靠性、成品率，而且巨大的应力会造成GaN厚膜和异质衬底裂成碎片，因而无法应用。
异质衬底如蓝宝石或硅上外延氮化镓时要经历升温-外延-降温的过程，外延失配起源于异质衬底和氮化镓晶格常数的不同产生的晶格失配，热失配起源于外延过程中升温或降温时因为二者热膨胀系数的不同导致的热应力。无论是采用何种异质外延设备，高温条件下外延完成后，氮化镓薄膜从大于1000摄氏度的高温降至室温的过程中产生的热失配应力，远大于初始高温条件下外延时产生的晶格失配。因此，生长氮化镓厚膜后降温过程产生的应力会导致样品弯曲、氮化镓薄膜产生裂纹甚至碎裂。
控制硅上氮化镓外延应力的方法有很多，比如低温氮化铝缓冲层、高低温氮化铝缓冲层、两步法生长等。但是这些方法不能完全消除应力，需要创新性的思路来研发低成本、工艺简单、高成品率的技术和方法来获得低应力氮化镓薄膜。
发明内容
本发明的目的是提供一种高效制备氮化镓衬底的方法。
本发明采取的技术方案为：
一种高效制备氮化镓衬底的方法，其特征在于：在硅衬底正反两面上用卤化物气相外延法生长氮化镓厚膜，控制生长条件，使双面氮化镓厚膜的厚度基本相同，碱溶液或酸溶液腐蚀去除硅衬底，得到两片氮化镓厚膜衬底。
优选的，在硅衬底正反两面先生长缓冲层，再用卤化物气相外延法生长氮化镓厚膜。
优选的，所述缓冲层为氮化镓层，或者氮化铝层。
优选的，其步骤包括：
(1)清洗硅衬底；
(2)将硅衬底置于HVPE反应器中，低温区升温至850～1000℃，高温区升温至450～650℃，开始在硅衬底双面生长氮化镓，厚度为100-1000nm；
(3)氮化镓的生长完成后，保持氨气流量不变，关闭氯化氢，高温区升温至1000～1100℃，调整氨气流量，开启氯化氢，开始双面生长氮化镓厚膜，生长到所需的厚度后，关闭氨气和氯化氢，缓慢降至室温(降温速率10-20℃/分钟)，取出样品；
(4)将样品置于碱溶液或酸溶液中，腐蚀去除硅衬底，得到两片氮化镓厚膜。
优选的，步骤(2)中气体流量分别：NH3流量为1000sccm,NH3载气氮气流量为2000sccm，通入镓舟的HCl流量为5-10sccm，HCl载气氮气为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压。
优选的，步骤(3)中气体流量分别：NH3流量为1500sccm,NH3载气氮气流量为1000sccm，通入镓舟的HCl流量为20-100sccm，HCl载气氮气流量为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压。
优选的，其步骤包括：
(1)清洗硅衬底；
(2)在硅衬底双面沉积氮化铝薄膜，厚度为100-1000nm，得到硅基氮化铝模板；
(3)将硅基氮化铝模板置于HVPE反应器中，在氨气气氛保护下开始升温，低温区升温至850-900℃，高温区升温至1000～1100℃，温度稳定10分钟后，开启氯化氢，开始双面生长氮化镓厚膜，生长到所需的厚度后，关闭氨气和氯化氢，缓慢降至室温，取出样品；
(4)将样品置于碱或酸溶液中，腐蚀去除硅衬底，得到两片氮化镓厚膜。
优选的，所述步骤(2)中在硅衬底双面沉积氮化铝薄膜的方法为金属有机物化学气相沉积、脉冲激光沉积、卤化物气相外延、磁控溅射等生长方法。
优选的，所述步骤(3)中气体流量分别：NH3流量为2500sccm,NH3载气流量为1000sccm，通入镓舟的HCl流量为20-100sccm，HCl载气流量为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压。
所述酸溶液为氢氟酸与硝酸混合溶液，所述碱溶液为氢氧化钠溶液或氢氧化钾溶液。
因现有的GaN一般生长在异质衬底如蓝宝石或硅片等上面，晶格失配和热失配会引起GaN外延层中存在较大的应力，无论采用机械抛光或者激光剥离去除异质衬底，应力仍然存在于GaN材料中。应力的存在会造成GaN基材料和器件性能的降低。本发明提出了利用利用硅衬底在正反两面同时外延GaN厚膜，控制生长条件使得两面外延的氮化镓厚度相等或相近、分布均匀，这样两面氮化镓对于硅衬底的应力减弱或相互抵消，从而得到低应力高质量的GaN厚膜的方法。生长完成后的样品在碱溶液或酸溶液中进行腐蚀即可得到2片氮化镓衬底。本发明方法步骤简单，不仅可以实现低应力氮化镓薄膜外延，而且可以实现多片同时生长，每一片衬底可以同时产出两片GaN厚膜，提高产量，且在现有HVPE反应器中即可进行，无需对设备进行大的改进。
附图说明
图1为本发明的GaN厚膜在硅衬底上双面生长的结构示意图。
图2为实施例1中在立式HVPE反应器中生长GaN薄膜的示意图。
图3为实施例2中在卧式HVPE反应器中生长GaN薄膜的示意图。
具体实施方式
本发明无需改变原有HVPE反应腔体结构。HVPE反应室由腔体管和多支气体导管组成，气体导管位于腔体管的入口部份，用于将反应气体送至生长区的外延生长衬底处，加热系统采用电阻炉或者射频加热方式均可。一般为双温区结构，分为金属源区(低温区)和生长区(高温区)。HCl和金属源反应，生成的气体产物进入生长区，在衬底表面和NH3混合发生反应，形成GaN。尾气及反应尘埃通过抽气系统抽出。金属源区温度从850-1000摄氏度(生长GaN厚膜时温度一般为850-900摄氏度)，生长区温度从450-1100摄氏度(生长GaN厚膜时温度一般为1000-1100摄氏度)。载气气体导管在周围分布。载气采用氮气或者氩气或者氢气及氢气和氮气混合气体。
实施例1
一种高效制备低应力高质量GaN衬底的方法，其步骤包括：
1、对2英寸硅衬底进行清洗和处理，经过丙酮、乙醇超声清洗5分钟，用氢氟酸去除表面氧化物，去离子水冲洗及高纯氮气吹干处理。
2、硅衬底放入立式HVPE反应器中后，低温区升温至850℃，高温区升温至600℃，在此温度下生长GaN层。气体流量分别：NH3流量为1000sccm,NH3载气氮气流量为2000sccm，通入镓舟的HCl流量为10sccm，HCl载气氮气流量为500sccm。总氮气为15000sccm。反应腔体压力1个大气压。生长时间1分钟。
3、低温GaN层生长完成后，保持氨气流量不变，关闭氯化氢。高温区升温至1000℃，开启氯化氢，即可开始生长GaN。气体流量分别：NH3流量为1500sccm,NH3载气氮气流量为1000sccm，通入镓舟的HCl流量为20sccm，HCl载气氮气流量为500sccm。总氮气为15000sccm。反应腔体压力1个大气压。
4、生长4小时后，关闭氨气和氯化氢，按照10℃/分钟速率缓慢降至室温，取出样品。本实施例中生长速率为100微米/小时。将样品置于的1M的氢氧化钠或氢氧化钾溶液中，放置30-60分钟后即可去除硅衬底，得到2片氮化镓衬底。适当温度的碱溶液可以更快的去除硅衬底。
实施例2
一种高效制备低应力高质量GaN衬底的方法，其步骤包括：
1、2英寸硅衬底，在其上采用其他方法例如使用MOCVD、PLD、HVPE、磁控溅射镀膜设备等双面外延氮化铝，得到硅基氮化铝模板。
2、硅基氮化铝模板放入卧式HVPE反应器中后，低温区升温至900℃，高温区升温至1100℃，在此温度下生长GaN。气体流量分别：NH3流量为1500sccm,NH3载气为氮气，流量为1000sccm；通入镓舟的HCl流量为20sccm，HCl载气为氮气，流量为500sccm。总氮气为15000sccm。反应腔体压力1个大气压。
3、生长4小时后，关闭氨气和氯化氢，按照20℃/分钟速率缓慢降至室温，取出样品。本实施例中生长速率为100微米/小时。
将样品置于50％氢氟酸+70％硝酸1：1混合溶液中，放置15分钟后即可去除硅衬底，得到2片氮化镓衬底。
Claims (10)
1.一种高效制备氮化镓衬底的方法，其特征在于：在硅衬底正反两面上用卤化物气相外延法生长氮化镓厚膜，控制生长条件，使双面氮化镓厚膜的厚度基本相同，酸溶液或碱溶液腐蚀去除硅衬底，得到两片氮化镓厚膜衬底。
2.根据权利要求1所述的高效制备氮化镓衬底的方法，其特征在于：在硅衬底正反两面先生长缓冲层，再用卤化物气相外延法生长氮化镓厚膜。
3.根据权利要求2所述的高效制备氮化镓衬底的方法，其特征在于：所述缓冲层为氮化镓缓冲层，或者氮化铝缓冲层。
4.根据权利要求3所述的高效制备氮化镓衬底的方法，其特征在于：其步骤包括：
(1)清洗硅衬底；
(2)将硅衬底置于HVPE反应器中，低温镓源区升温至850～1000℃(常用温度850℃)，高温生长区升温至450～650℃，开始在硅衬底双面生长氮化镓，厚度为100-1000nm；
(3)低温氮化镓层的生长完成后，保持氨气流量不变，关闭氯化氢，高温区升温至1000～1100℃，调节氨气流量，开启氯化氢，开始双面生长氮化镓厚膜，生长到所需的厚度后，关闭氨气和氯化氢，缓慢降至室温，降温速率为10-20℃/分钟，取出样品；
(4)将样品置于酸溶液或碱溶液中，腐蚀去除硅衬底，得到两片氮化镓厚膜。
5.根据权利要求4所述的高效制备氮化镓衬底的方法，其特征在于：步骤(2)中气体流量分别：NH3流量为1000sccm,NH3载气氮气流量为2000sccm，通入镓舟的HCl流量为5-10sccm，HCl载气氮气流量为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压，缓冲层生长时间为1-5分钟。
6.根据权利要求4所述的高效制备氮化镓衬底的方法，其特征在于：步骤(3)中气体流量分别：NH3流量为2500sccm,NH3载气氮气流量为1000sccm，通入镓舟的HCl流量为20-100sccm，HCl载气氮气流量为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压。
7.根据权利要求3所述的高效制备氮化镓衬底的方法，其特征在于：其步骤包括：
(1)清洗硅衬底；
(2)在硅衬底双面沉积氮化铝薄膜，厚度为100-1000nm，得到硅基氮化铝模板；
(3)将硅基氮化铝模板置于HVPE反应器中，在氨气保护下开始升温，低温镓源区升温至850-1000℃，高温区升温至1000～1100℃，稳定一段时间后，开启氯化氢，开始双面生长氮化镓厚膜，生长到所需的厚度后，关闭氨气和氯化氢，缓慢降至室温，降温速率为10-20℃/分钟，取出样品；
(4)将样品置于碱溶液或酸溶液中，腐蚀去除硅衬底，得到两片氮化镓厚膜。
8.根据权利要求7所述的高效制备氮化镓衬底的方法，其特征在于：所述步骤(2)中在硅衬底双面沉积氮化铝薄膜的方法为金属有机物化学气相沉积、脉冲激光沉积、卤化物气相外延、磁控溅射生长方法。
9.根据权利要求7所述的高效制备氮化镓衬底的方法，其特征在于：所述步骤(3)中气体流量分别：NH3流量为2500sccm,NH3载气流量为1000sccm，通入镓舟的HCl流量为20-100sccm，HCl载气流量为500sccm，总氮气为15000sccm，反应腔体压力为一个大气压。
10.根据权利要求4或7所述的高效制备氮化镓衬底的方法，其特征在于：所述酸溶液为氢氟酸与硝酸混合溶液，所述碱溶液为氢氧化钠溶液或氢氧化钾溶液。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113345798A (zh) * | 2021-06-01 | 2021-09-03 | 中科汇通(内蒙古)投资控股有限公司 | 一种SiC基片外延制备GaN的方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1779910A (zh) * | 2004-11-25 | 2006-05-31 | 中国科学院半导体研究所 | 在硅衬底上生长氮化镓自支撑衬底材料的方法 |
| US20070243652A1 (en) * | 2006-04-14 | 2007-10-18 | Applied Materials, Inc. | Stacked-substrate processes for production of nitride semiconductor structures |
| CN104143497A (zh) * | 2013-05-08 | 2014-11-12 | 上海华虹宏力半导体制造有限公司 | GaN外延或GaN衬底的制作方法 |
| CN104178806A (zh) * | 2014-08-20 | 2014-12-03 | 中国科学院半导体研究所 | 悬挂式双面外延生长装置 |
| CN105845798A (zh) * | 2015-01-16 | 2016-08-10 | 北京大学 | 无翘曲ⅲ族氮化物复合衬底的制备方法和衬底放置装置 |
-
2020
- 2020-10-21 CN CN202011129338.9A patent/CN112259446A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1779910A (zh) * | 2004-11-25 | 2006-05-31 | 中国科学院半导体研究所 | 在硅衬底上生长氮化镓自支撑衬底材料的方法 |
| US20070243652A1 (en) * | 2006-04-14 | 2007-10-18 | Applied Materials, Inc. | Stacked-substrate processes for production of nitride semiconductor structures |
| CN104143497A (zh) * | 2013-05-08 | 2014-11-12 | 上海华虹宏力半导体制造有限公司 | GaN外延或GaN衬底的制作方法 |
| CN104178806A (zh) * | 2014-08-20 | 2014-12-03 | 中国科学院半导体研究所 | 悬挂式双面外延生长装置 |
| CN105845798A (zh) * | 2015-01-16 | 2016-08-10 | 北京大学 | 无翘曲ⅲ族氮化物复合衬底的制备方法和衬底放置装置 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113345798A (zh) * | 2021-06-01 | 2021-09-03 | 中科汇通(内蒙古)投资控股有限公司 | 一种SiC基片外延制备GaN的方法 |
| CN113345798B (zh) * | 2021-06-01 | 2022-07-12 | 中科汇通(内蒙古)投资控股有限公司 | 一种SiC基片外延制备GaN的方法 |
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